JPWO2012131917A1 - Honeycomb structure and method for manufacturing honeycomb structure - Google Patents

Abstract

The honeycomb structure of the present invention is a honeycomb structure having a honeycomb unit in which a plurality of through holes are arranged in parallel in the longitudinal direction with partition walls, the honeycomb unit being ion-exchanged with iron ions And a raw material paste containing an inorganic binder is extruded and fired, and the zeolite has a specific surface area of 500 m2 / g or more and 800 m2 / g or less, and an outer surface area of 40 m2 / g or more and 80 m2 / g or less. It is.

Description

  The present invention relates to a honeycomb structure and a method for manufacturing a honeycomb structure.

  2. Description of the Related Art Conventionally, an SCR (Selective Catalytic Reduction) system that uses ammonia to reduce NOx to nitrogen and water is known as one of systems for purifying automobile exhaust gas.

  In addition, zeolite is known as a material that adsorbs ammonia in the SCR system.

  Patent Document 1 discloses a honeycomb structure having a honeycomb unit including zeolite, inorganic fibers and / or whiskers, and an inorganic binder.

International Publication No. 06/137149

  However, there is a need for a honeycomb structure that is further superior in NOx purification performance than the honeycomb structure disclosed in Patent Document 1. For this reason, it is conceivable to use zeolite such as β-type zeolite that has been ion-exchanged with iron ions that are excellent in NOx purification performance as the material of the honeycomb unit constituting the honeycomb structure.

  At this time, there is a problem that the purification performance of NOx is not sufficiently improved even if β-type zeolite having a large specific surface area and a large amount of ion exchange ion-exchanged with iron ions is used.

  An object of the present invention is to provide a honeycomb structure excellent in NOx purification performance and a method for manufacturing the honeycomb structure in view of the problems of the above-described conventional technology.

The honeycomb structure of the present invention is a honeycomb structure having a honeycomb unit in which a plurality of through-holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and the honeycomb unit is an ion exchanged by iron ions The zeolite has a specific surface area of 500 m ² / g or more and 800 m ² / g or less, and an outer surface area of 40 m ² / g or more and 80 m. ² / g or less.

The zeolite preferably has an ion exchange amount of 1.6% by mass or more ion-exchanged with iron ions.

When the ion exchange amount, specific surface area, and outer surface area that are ion-exchanged with iron ions of the zeolite are M [mass%], S ₁ [m ² / g], and S ₂ [m ² / g], respectively, It is desirable to satisfy 0.25 ≦ M × (S ₂ / S ₁ ) ≦ 0.60.

The zeolite preferably has an average particle size of secondary particles of 3 μm to 5 μm.

The zeolite is preferably a β-type zeolite.

The raw material paste preferably further includes one or more selected from the group consisting of inorganic fibers, scale-like substances, tetrapot-like substances, and three-dimensional needle-like substances.

The honeycomb structure of the present invention preferably has a plurality of the honeycomb units.

A method for manufacturing a honeycomb structure according to the present invention is a method for manufacturing a honeycomb structure having a honeycomb unit in which a plurality of through holes are arranged in parallel in a longitudinal direction with partition walls being separated by iron ions. A step of extruding a raw material paste containing zeolite and an inorganic binder, and a step of firing the extruded raw material paste to produce the honeycomb unit, wherein the zeolite has a specific surface area of 500 m ² / g or more. 800 m ² / g or less, and the outer surface area is 40 m ² / g or more and 80 m ² / g or less.

The zeolite preferably has an ion exchange amount of 1.6% by mass or more ion-exchanged with iron ions.

When the ion exchange amount, specific surface area, and outer surface area that are ion-exchanged with iron ions of the zeolite are M [mass%], S ₁ [m ² / g], and S ₂ [m ² / g], respectively, It is desirable to satisfy 0.25 ≦ M × (S ₂ / S ₁ ) ≦ 0.60.

The zeolite preferably has an average particle size of secondary particles of 3 μm to 5 μm.

The zeolite is preferably a β-type zeolite.

The raw material paste preferably further includes one or more selected from the group consisting of inorganic fibers, scale-like substances, tetrapot-like substances, and three-dimensional needle-like substances.

The honeycomb structure preferably includes a plurality of the honeycomb units.

  According to the present invention, it is possible to provide a honeycomb structure excellent in NOx purification performance and a method for manufacturing the honeycomb structure.

It is a perspective view which shows an example of the honeycomb structure of this invention. It is sectional drawing which shows an example of the exhaust gas purification apparatus of this invention. It is a perspective view which shows the other example of the honeycomb structure of this invention. Fig. 4 is a perspective view showing a honeycomb unit constituting the honeycomb structure of Fig. 3.

  Next, the form for implementing this invention is demonstrated with drawing.

  FIG. 1 shows an example of the honeycomb structure of the present invention. The honeycomb structure 10 includes a single honeycomb unit 11 in which a plurality of through holes 11a are arranged in parallel in the longitudinal direction with a partition wall 11b interposed therebetween. The honeycomb unit 11 is manufactured by extruding and firing a raw material paste containing zeolite and an inorganic binder ion-exchanged with iron ions. Further, an outer peripheral coat layer 12 is formed on the outer peripheral surface excluding both end surfaces of the honeycomb unit 11.

  Hereinafter, zeolite means zeolite contained in the raw material paste.

The specific surface area of the zeolite is 500~800m ² / g, preferably from ^{500~600m 2 / g, 535~538m 2 /} g is more preferable. When the specific surface area of the zeolite is less than 500 m ² / g, the number of pores in the honeycomb unit 11 is reduced, so that the exhaust gas does not easily enter the partition walls 11b of the honeycomb unit 11 and the zeolite is effective for purifying NOx. Is no longer used. On the other hand, it is difficult to produce a zeolite having a specific surface area exceeding 800 m ² / g.

The specific surface area of the zeolite can be measured by BET one point method (N ₂ adsorption method). Moreover, when measuring the specific surface area of zeolite, for example, an automatic specific surface area / pore distribution measuring device Tristar 3000 (manufactured by Shimadzu Corporation) can be used.

External surface area of the zeolite is 40 to 80 m ² / g, preferably from ^{40~60m 2 / g, 40~52m 2 /} g is more preferable. If the external surface area of the zeolite is less than 40 m ² / g, the ratio of the external surface area to the specific surface area of the zeolite will be small, that is, the number of pores existing on the surface of the zeolite will increase, making the zeolite effective for purifying NOx. It will not be used. On the other hand, it is difficult to produce a zeolite having an outer surface area exceeding 80 m ² / g.

The outer surface area of the zeolite can be measured by using a t- plot method (N ₂ adsorption method). Moreover, when measuring the outer surface area of zeolite, for example, an automatic specific surface area / pore distribution measuring device Tristar 3000 (manufactured by Shimadzu Corporation) can be used.

  Zeolite preferably has an ion exchange amount of 1.6% by mass or more that is ion-exchanged with iron ions. When the ion exchange amount ion-exchanged with the iron ions of the zeolite is less than 1.6% by mass, the NOx purification performance is not sufficiently improved.

  In addition, since it is difficult to produce a zeolite having an ion exchange amount that is ion-exchanged with iron ions exceeding 5.0% by mass, the ion exchange amount that is ion-exchanged with iron ions is 1.6. More preferably, it is -5.0 mass%. Moreover, it is more preferable that the ion exchange amount of the zeolite ion-exchanged with iron ions is 3.6 to 4.7% by mass.

  The zeolite may be further ion-exchanged with a transition metal ion or the like that can improve the NOx purification performance.

When the ion exchange amount, the specific surface area, and the outer surface area that are ion-exchanged by the iron ions of the zeolite are M [mass%], S ₁ [m ² / g], and S ₂ [m ² / g], respectively, Formula 0 .25 ≦ M × (S ₂ / S ₁ ) ≦ 0.60
Preferably satisfying the formula 0.27 ≦ M × (S ₂ / S ₁ ) ≦ 0.45
It is more preferable to satisfy. When M × (S ₂ / S ₁ ) is less than 0.25% by mass, the NOx purification performance is not sufficiently improved. On the other hand, it is difficult to produce a zeolite having M × (S ₂ / S ₁ ) exceeding 0.60 mass%.

  The zeolite preferably has an average secondary particle size of 3 to 5 μm. If the average particle size of the secondary particles of the zeolite is less than 3 μm, the exhaust gas hardly enters the partition walls 11b of the honeycomb unit 11, and the zeolite is not effectively used for NOx purification. On the other hand, if the average particle size of the secondary particles of the zeolite exceeds 5 μm, the number of pores in the honeycomb unit 11 decreases, so that the exhaust gas does not easily enter the partition walls 11b of the honeycomb unit 11 and the zeolite is NOx. It will not be used effectively for purification.

  Although it does not specifically limit as a zeolite, A beta type zeolite, ZSM-5 type zeolite, etc. are mentioned, You may use 2 or more types together. Among these, β-type zeolite is preferable because of its excellent NOx purification performance.

  The honeycomb unit 11 preferably has a zeolite content per apparent volume of 230 to 400 g / L. If the zeolite content per apparent volume of the honeycomb unit 11 is less than 230 g / L, it is necessary to increase the apparent volume of the honeycomb unit 11 in order to improve the NOx purification performance. On the other hand, if the content of zeolite per apparent volume of the honeycomb unit 11 exceeds 400 g / L, the strength of the honeycomb unit 11 becomes insufficient or the aperture ratio of the honeycomb unit 11 becomes small.

  The inorganic binder contained in the raw material paste is not particularly limited, and examples thereof include alumina sol, silica sol, titania sol, water glass, sepiolite, attapulgite, and boehmite, and two or more kinds may be used in combination.

  The content of the solid content of the inorganic binder in the solid content of the raw material paste is preferably 5 to 30% by mass, and more preferably 10 to 20% by mass. If the content of the solid content of the inorganic binder in the solid content of the raw material paste is less than 5% by mass, the strength of the honeycomb unit 11 is lowered. On the other hand, when the content of the solid content of the inorganic binder in the solid content of the raw material paste exceeds 30% by mass, it becomes difficult to extrude the honeycomb unit 11.

  In order to improve the strength of the honeycomb unit 11, the raw material paste preferably further includes at least one selected from the group consisting of inorganic fibers, scale-like substances, tetrapot-like substances, and three-dimensional needle-like substances.

  The material constituting the inorganic fiber contained in the raw material paste is not particularly limited, and examples thereof include alumina, silica, silicon carbide, silica alumina, glass, potassium titanate, aluminum borate and the like. Good.

  The aspect ratio of the inorganic fibers contained in the raw material paste is preferably 2 to 1000, more preferably 5 to 800, and still more preferably 10 to 500. When the aspect ratio of the inorganic fibers contained in the raw material paste is less than 2, the effect of improving the strength of the honeycomb unit 11 is reduced. On the other hand, if the aspect ratio of the inorganic fiber contained in the raw material paste exceeds 1000, the die may be clogged when the honeycomb unit 11 is extruded, or the inorganic fiber breaks and the strength of the honeycomb unit 11 is increased. The effect to improve becomes small.

  The scaly substance means a flat substance, preferably having a thickness of 0.2 to 5.0 μm, preferably having a maximum length of 10 to 160 μm, and a ratio of the maximum length to the thickness of 3 It is preferable that it is -250.

  Although it does not specifically limit as a material which comprises the scale-like substance contained in raw material paste, Glass, muscovite, alumina, a silica etc. are mentioned, You may use 2 or more types together.

  The tetrapot-like substance means a substance in which the needle-like portion extends three-dimensionally. The average needle-like length of the needle-like portion is preferably 5 to 30 μm, and the average diameter of the needle-like portion is 0.5. It is preferable that it is -5.0 micrometers.

  Although it does not specifically limit as a material which comprises the tetrapod-like substance contained in a raw material paste, Zinc oxide etc. are mentioned, You may use 2 or more types together.

  The three-dimensional acicular substance means a substance in which the acicular parts are bonded by an inorganic compound such as glass near the center of each acicular part, and the average acicular length of the acicular parts is 5 to 30 μm. It is preferable that the average diameter of the needle-shaped part is 0.5 to 5.0 μm.

  Further, the three-dimensional acicular substance may have a plurality of acicular portions that are three-dimensionally connected, and preferably has a diameter of 0.1 to 5.0 μm and a length of 0.3 to 5.0 μm. It is preferable that it is 30.0 micrometers, and it is preferable that ratio of the length with respect to a diameter is 1.4-50.0.

  The material constituting the three-dimensional acicular substance contained in the raw material paste is not particularly limited, and examples thereof include alumina, silica, silicon carbide, silica alumina, glass, potassium titanate, aluminum borate, boehmite, and the like. You may use together.

  The content of inorganic fiber, scale-like substance, tetrapot-like substance and three-dimensional needle-like substance in the solid content of the raw material paste is preferably 3 to 50% by mass, more preferably 3 to 30% by mass. -20 mass% is further more preferable. When the content of the inorganic fiber, the scale-like substance, the tetrapot-like substance, and the three-dimensional needle-like substance in the solid content of the raw material paste is less than 3% by mass, the effect of improving the strength of the honeycomb unit 11 becomes small. On the other hand, when the content of the inorganic fiber, scale-like substance, tetrapot-like substance and three-dimensional needle-like substance in the solid content of the raw material paste exceeds 50% by mass, the content of zeolite in the honeycomb unit 11 decreases. NOx purification performance decreases.

  The honeycomb unit 11 preferably has a porosity of 20 to 50%. When the porosity of the honeycomb unit 11 is less than 20%, the exhaust gas hardly enters the partition walls 11b of the honeycomb unit 11 and the zeolite is not effectively used for NOx purification. On the other hand, when the porosity of the honeycomb unit 11 exceeds 50%, the strength of the honeycomb unit 11 becomes insufficient.

  The porosity of the honeycomb unit 11 can be measured using a mercury intrusion method.

  The honeycomb unit 11 preferably has an opening ratio of a cross section perpendicular to the longitudinal direction of 50 to 75%. If the opening ratio of the cross section perpendicular to the longitudinal direction of the honeycomb unit 11 is less than 50%, the zeolite is not effectively used for purification of NOx. On the other hand, if the opening ratio of the cross section perpendicular to the longitudinal direction of the honeycomb unit 11 exceeds 75%, the strength of the honeycomb unit 11 becomes insufficient.

In the honeycomb unit 11, the density of the through holes 11 a having a cross section perpendicular to the longitudinal direction is preferably 31 to 155 / cm ² . When the density of the through-holes 11a having a cross section perpendicular to the longitudinal direction of the honeycomb unit 11 is less than 31 / cm ² , it becomes difficult for the zeolite and the exhaust gas to come into contact with each other, and the NOx purification performance is lowered. On the other hand, when the density of the through holes 11a having a cross section perpendicular to the longitudinal direction of the honeycomb unit 11 exceeds 155 / cm ² , the pressure loss of the honeycomb structure 10 increases.

  The thickness of the partition wall 11b of the honeycomb unit 11 is preferably 0.1 to 0.4 mm, and more preferably 0.1 to 0.3 mm. When the thickness of the partition wall 11b of the honeycomb unit 11 is less than 0.1 mm, the strength of the honeycomb unit 11 decreases. On the other hand, if the thickness of the partition wall 11b of the honeycomb unit 11 exceeds 0.4 mm, the exhaust gas hardly enters the partition wall 11b of the honeycomb unit 11, and the zeolite is not effectively used for NOx purification.

  The outer peripheral coat layer 12 preferably has a thickness of 0.1 to 2.0 mm. When the thickness of the outer peripheral coat layer 12 is less than 0.1 mm, the effect of improving the strength of the honeycomb structure 10 becomes insufficient. On the other hand, when the thickness of the outer peripheral coat layer 12 exceeds 2.0 mm, the content of zeolite per unit volume of the honeycomb structure 10 decreases, and the NOx purification performance decreases.

  The shape of the honeycomb structure 10 is not limited to a cylindrical shape, and examples thereof include a prismatic shape, an elliptical cylindrical shape, a long cylindrical shape, and a rounded chamfered prismatic shape (for example, a rounded chamfered triangular prism shape).

  The shape of the through hole 11a is not limited to a quadrangular prism shape, and examples thereof include a triangular prism shape and a hexagonal prism shape.

  Next, an example of a method for manufacturing the honeycomb structure 10 will be described. First, it contains a zeolite ion exchanged with iron ions and an inorganic binder, and if necessary, one or more selected from the group consisting of inorganic fibers, scaly substances, tetrapot-like substances and three-dimensional acicular substances A columnar honeycomb formed body in which a plurality of through holes are arranged in parallel in the longitudinal direction with a partition wall therebetween is manufactured by using the raw material paste that is included.

  Moreover, you may add an organic binder, a dispersion medium, a shaping | molding adjuvant, etc. to a raw material paste suitably as needed.

  Although it does not specifically limit as an organic binder, Methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, polyethyleneglycol, a phenol resin, an epoxy resin etc. are mentioned, You may use 2 or more types together. In addition, it is preferable that the addition amount of an organic binder is 1-10% with respect to the total mass of a zeolite, an inorganic binder, an inorganic fiber, a scale-like substance, a tetrapot-like substance, and a three-dimensional acicular substance.

  Although it does not specifically limit as a dispersion medium, Alcohol, such as water, organic solvents, such as benzene, methanol, etc. are mentioned, You may use 2 or more types together.

  Although it does not specifically limit as a shaping | molding adjuvant, Ethylene glycol, dextrin, a fatty acid, fatty acid soap, a polyalcohol etc. are mentioned, You may use together 2 or more types.

  When preparing a raw material paste, it is preferable to mix and knead, and it may mix using a mixer, an attritor, etc., and may knead using a kneader.

  Next, the honeycomb formed body is dried by using a dryer such as a microwave dryer, a hot air dryer, a dielectric dryer, a vacuum dryer, a vacuum dryer, or a freeze dryer to produce a honeycomb dried body.

  Further, the honeycomb dried body is degreased to produce a honeycomb degreased body. The degreasing conditions can be appropriately selected depending on the type and amount of the organic substance contained in the dried honeycomb body, but it is preferably 2 hours at 400 ° C.

  Next, the honeycomb degreased body is fired to produce a columnar honeycomb unit 11. The firing temperature is preferably 600 to 1200 ° C, more preferably 600 to 1000 ° C. When the firing temperature is less than 600 ° C., the sintering does not proceed and the strength of the honeycomb unit 11 is lowered. On the other hand, if the firing temperature exceeds 1200 ° C., the sintering proceeds too much and the reaction sites of the zeolite decrease.

  Next, the outer peripheral coat layer paste is applied to the outer peripheral surface excluding both end surfaces of the columnar honeycomb unit 11.

  Although it does not specifically limit as a paste for outer periphery coating layers, The mixture of an inorganic binder and an inorganic particle, the mixture of an inorganic binder and an inorganic fiber, the mixture of an inorganic binder, an inorganic particle, and an inorganic fiber etc. are mentioned.

  Although it does not specifically limit as an inorganic binder contained in the paste for outer periphery coating layers, A silica sol, an alumina sol, etc. are mentioned, You may use 2 or more types together. Among these, it is preferable to add as silica sol.

  The material constituting the inorganic particles contained in the outer peripheral coat layer paste is not particularly limited, but examples thereof include carbides such as silicon carbide, nitrides such as silicon nitride and boron nitride, and two or more kinds may be used in combination. . Of these, silicon carbide is preferred because of its excellent thermal conductivity.

  Although it does not specifically limit as a material which comprises the inorganic fiber contained in the paste for outer periphery coating layers, A silica alumina, a mullite, an alumina, a silica etc. are mentioned, You may use 2 or more types together. Of these, alumina is preferable.

  The outer periphery coating layer paste may further contain an organic binder.

  Although it does not specifically limit as an organic binder contained in the paste for outer periphery coating layers, Polyvinyl alcohol, methylcellulose, ethylcellulose, carboxymethylcellulose, etc. are mentioned, You may use 2 or more types together.

  The outer periphery coat layer paste may further contain balloons, pore formers, and the like, which are fine hollow spheres of oxide ceramics.

  The balloon contained in the outer peripheral coat layer paste is not particularly limited, and examples thereof include alumina balloons, glass micro balloons, shirasu balloons, fly ash balloons, mullite balloons and the like, and two or more kinds may be used in combination. Among these, an alumina balloon is preferable.

  Although it does not specifically limit as a pore making material contained in the paste for outer periphery coating layers, A spherical acrylic particle, a graphite, etc. are mentioned, You may use 2 or more types together.

  Next, the honeycomb unit 11 to which the outer peripheral coat layer paste is applied is dried and solidified to produce a columnar honeycomb structure 10. At this time, when the outer peripheral coat layer paste contains an organic binder, it is preferably degreased. The degreasing conditions can be appropriately selected depending on the kind and amount of the organic matter, but it is preferably 20 minutes at 700 ° C.

  Note that, instead of zeolite ion-exchanged with iron ions, zeolite not ion-exchanged with iron ions is used to place the honeycomb unit 11 or the honeycomb structure 10 in an aqueous solution containing iron ions (for example, an aqueous silver nitrate solution). The zeolite may be ion-exchanged by immersing it in.

  FIG. 2 shows an example of the exhaust gas purifying apparatus of the present invention. The exhaust gas purification apparatus 100 can be manufactured by canning the metal container (shell) 30 in a state where the holding sealing material 20 is disposed on the outer peripheral portion of the honeycomb structure 10. Further, the exhaust gas purification apparatus 100 includes an injection nozzle that injects ammonia or a compound that decomposes to generate ammonia into a pipe (not shown) on the upstream side of the honeycomb structure 10 with respect to the direction in which the exhaust gas flows. Injecting means (not shown) is provided. As a result, ammonia is added to the exhaust gas flowing through the pipe, so that NOx contained in the exhaust gas is reduced by the zeolite contained in the honeycomb unit 11.

  The compound that decomposes to generate ammonia is not particularly limited as long as it can be heated by exhaust gas in a pipe and generate ammonia, but urea water is preferable because of excellent storage stability.

  The urea water is heated by the exhaust gas in the pipe and hydrolyzes to generate ammonia.

  FIG. 3 shows another example of the honeycomb structure of the present invention. In the honeycomb structure 10 ′, a plurality of honeycomb units 11 ′ (see FIG. 4) in which a plurality of through holes 11 a are arranged in parallel in the longitudinal direction with the partition walls 11 b interposed therebetween are bonded via an adhesive layer 13. Other than this, the configuration is the same as that of the honeycomb structure 10.

The honeycomb unit 11 ′ preferably has a cross-sectional area of 10 to 200 cm ² in a cross section perpendicular to the longitudinal direction. When the cross-sectional area of the cross section perpendicular to the longitudinal direction of the honeycomb unit 11 ′ is less than 10 cm ² , the pressure loss of the honeycomb structure 10 ′ increases. On the other hand, when the cross-sectional area of the cross section perpendicular to the longitudinal direction of the honeycomb unit 11 ′ exceeds 200 cm ² , the strength against the thermal stress generated in the honeycomb unit 11 ′ becomes insufficient.

  The honeycomb unit 11 ′ has the same configuration as the honeycomb unit 11 except for the cross-sectional area of the cross section perpendicular to the longitudinal direction.

  The adhesive layer 13 preferably has a thickness of 0.5 to 2.0 mm. When the thickness of the adhesive layer 13 is less than 0.5 mm, the adhesive strength of the honeycomb unit 11 ′ becomes insufficient. On the other hand, when the thickness of the adhesive layer 13 exceeds 2.0 mm, the pressure loss of the honeycomb structure 10 ′ increases.

  Next, an example of a method for manufacturing the honeycomb structure 10 'will be described. First, in the same manner as the honeycomb structure 10, a quadrangular columnar honeycomb unit 11 'is manufactured. Next, an adhesive layer paste is applied to the outer peripheral surface excluding both end faces of the honeycomb unit 11 ′, and the honeycomb units 11 ′ are sequentially bonded and dried and solidified to produce an aggregate of the honeycomb units 11 ′.

  Although it does not specifically limit as a paste for contact bonding layers, The mixture of an inorganic binder and an inorganic particle, the mixture of an inorganic binder and an inorganic fiber, the mixture of an inorganic binder, an inorganic particle, and an inorganic fiber etc. are mentioned.

  Although it does not specifically limit as an inorganic binder contained in the paste for contact bonding layers, A silica sol, an alumina sol, etc. are mentioned, You may use 2 or more types together. Among these, it is preferable to add as silica sol.

  The material constituting the inorganic particles contained in the adhesive layer paste is not particularly limited, and examples thereof include carbides such as silicon carbide, nitrides such as silicon nitride and boron nitride, and two or more kinds may be used in combination. Of these, silicon carbide is preferred because of its excellent thermal conductivity.

  Although it does not specifically limit as a material which comprises the inorganic fiber contained in the paste for contact bonding layers, A silica alumina, mullite, an alumina, a silica, etc. are mentioned, You may use 2 or more types together. Of these, alumina is preferable.

  The adhesive layer paste may contain an organic binder.

  Although it does not specifically limit as an organic binder contained in the paste for contact bonding layers, Polyvinyl alcohol, methylcellulose, ethylcellulose, carboxymethylcellulose etc. are mentioned, You may use 2 or more types together.

  The adhesive layer paste may further contain a balloon, a pore-forming agent, etc., which are fine hollow spheres of oxide ceramics.

  Although it does not specifically limit as a balloon contained in the paste for contact bonding layers, An alumina balloon, a glass micro balloon, a shirasu balloon, a fly ash balloon, a mullite balloon etc. are mentioned, You may use 2 or more types together. Among these, an alumina balloon is preferable.

  Although it does not specifically limit as a pore making material contained in the paste for contact bonding layers, A spherical acrylic particle, a graphite, etc. are mentioned, You may use 2 or more types together.

  Next, after the aggregate of the honeycomb units 11 ′ is cut into a cylindrical shape, the aggregate of the cylindrical honeycomb units 11 ′ is manufactured by polishing as necessary.

  Instead of cutting the aggregate of the honeycomb units 11 ′ into a columnar shape, the honeycomb unit 11 ′ whose cross section perpendicular to the longitudinal direction is formed into a predetermined shape is bonded to the columnar honeycomb unit 11 ′. You may produce the aggregate | assembly of. At this time, the shape of the cross section perpendicular to the longitudinal direction of the honeycomb unit 11 ′ is preferably a sector shape with a central angle of 90 °.

  Next, the outer peripheral coat layer paste is applied to the outer peripheral surface excluding both end surfaces of the aggregate of the cylindrical honeycomb units 11 ′.

  The outer periphery coating layer paste may be the same as or different from the adhesive layer paste.

  Next, a columnar honeycomb structure 10 ′ is produced by drying and solidifying the aggregate of columnar honeycomb units 11 ′ coated with the outer periphery coating layer paste. At this time, when an organic binder is contained in the adhesive layer paste and / or the outer peripheral coat layer paste, it is preferable to degrease. The degreasing conditions can be appropriately selected depending on the kind and amount of the organic matter, but it is preferably 20 minutes at 700 ° C.

  Note that the outer peripheral coat layer 12 may not be formed in the honeycomb structures 10 and 10 ′.

  In this embodiment, the part means part by mass.

[Example 1]
Β-type zeolite having a specific surface area of 535 m ² / g, an outer surface area of 40 m ² / g, and an average secondary particle size of 3 μm was immersed in an aqueous iron nitrate solution for ion exchange. ICPS-8100 (manufactured by Shimadzu Corporation) was used for ICP emission analysis to measure the amount of ion exchange that was ion-exchanged with the iron ions of the β-type zeolite, which was 3.6% by mass.

  2800 parts of the obtained β-type zeolite, 1120 parts of a mixture of 72% by weight of boehmite and 28% by weight of acetic acid, 270 parts of alumina fibers having an average fiber diameter of 6 μm and an average fiber length of 100 μm, 380 parts of methylcellulose, 310 parts of oleic acid Then, 2400 parts of ion-exchanged water was mixed and kneaded to prepare a raw material paste 1.

Next, the raw material paste 1 was extrusion-molded using an extruder to produce a regular quadrangular prism-shaped honeycomb formed body. Then, the honeycomb formed body was dried at 110 ° C. for 10 minutes using a microwave dryer and a hot air dryer, and then degreased at 400 ° C. for 5 hours. Next, the honeycomb unit 11 ′ was manufactured by firing at 700 ° C. for 2 hours. The honeycomb unit 11 ′ was a regular quadrangular prism shape with a side of 38 mm and a length of 150 mm, the density of the through holes 11 a was 65 / cm ² , and the thickness of the partition walls 11 b was 0.28 mm.

  Next, 767 parts of alumina fiber having an average fiber diameter of 0.5 μm and an average fiber length of 15 μm, 2500 parts of silica glass, 17 parts of carboxymethylcellulose, 600 parts of silica sol having a solid content of 30% by mass, and 167 parts of polyvinyl alcohol Part, 167 parts of surfactant and 17 parts of alumina balloon were mixed and kneaded to prepare an adhesive layer paste.

  The adhesive layer paste was applied to the outer peripheral surface excluding both ends of the honeycomb unit 11 ′ so that the thickness of the adhesive layer 13 was 2.0 mm, and 16 honeycomb units 11 ′ were adhered to each other at 150 ° C. Solidified for a minute. Next, a diamond cutter was used to cut into a cylindrical shape so that the cross section perpendicular to the longitudinal direction was substantially point-symmetric, and an aggregate of honeycomb units 11 ′ was produced.

  Furthermore, after applying the adhesive layer paste to the outer peripheral surface excluding both ends of the aggregate of the honeycomb unit 11 ′ so that the outer peripheral coat layer 12 has a thickness of 1.0 mm, the microwave dryer and the hot air dryer are applied. Then, the adhesive layer paste was dried and solidified at 150 ° C. for 10 minutes and degreased at 400 ° C. for 2 hours to prepare a cylindrical honeycomb structure 10 ′ having a diameter of 160 mm and a length of 150 mm.

[Example 2]
Except for using a β-type zeolite having a specific surface area of 538 m ² / g, an outer surface area of 52 m ² / g, and an average particle size of secondary particles of 3 μm, the ion exchange amount of the zeolite was changed to 4.7% by mass, In the same manner as in Example 1, a honeycomb structure 10 ′ was produced.

[Example 3]
A honeycomb structure 10 ′ was produced in the same manner as in Example 1 except that the ion exchange amount of zeolite was changed to 4.7% by mass.

[Comparative Example 1]
Except for using β-type zeolite having a specific surface area of 521 m ² / g, an outer surface area of 35 m ² / g, and an average particle size of secondary particles of 3 μm, the ion exchange amount of the zeolite was changed to 3.3% by mass, A honeycomb structure was manufactured in the same manner as in Example 1.

[Comparative Example 2]
Except for using a β-type zeolite having a specific surface area of 507 m ² / g, an outer surface area of 20 m ² / g, and an average particle size of secondary particles of 3 μm, the ion exchange amount of the zeolite was changed to 4.6% by mass, A honeycomb structure was manufactured in the same manner as in Example 1.

[Measurement of specific surface area and external surface area of zeolite]
Using an automatic specific surface area / pore distribution measuring device Tristar 3000 (manufactured by Shimadzu Corporation), a plot of the adsorption amount V [cm ³ (STP) · g ⁻¹ ] against the relative pressure P / P ₀ , that is, nitrogen absorption A desorption isotherm was created, and the specific surface area and outer surface area were determined using the BET single point method and the t-plot method. Specifically, the specific surface area is obtained from a plot of P / V (P ₀ -P) [g · cm ³ (STP) ⁻¹ ] against the relative pressure P / P ₀ , that is, a BET plot. plot of _P / V with respect to the thickness t [nm] of the adsorbent layer ^{(P 0 -P) [g ·} cm 3 (STP) -1], that is, determined from t- plot.

[Evaluation of NOx purification rate]
From the honeycomb units manufactured in Examples 1 to 3 and Comparative Examples 1 and 2, a regular square columnar sample having a side of 30 mm and a length of 30 mm was cut out using a diamond cutter.

Using a catalyst evaluation apparatus SIGU-2000 (manufactured by Horiba, Ltd.) while flowing a simulated gas at 200 ° C. at a space velocity (SV) of 35000 / h, the amount of NOx flowing out from the sample is measured, (NOx inflow amount−NOx outflow amount) / (NOx inflow amount) × 100
The NOx purification rate [%] expressed by Note that the constituent components of the simulated gas are nitrogen monoxide 210 ppm, nitrogen dioxide 70 ppm, ammonia 420 ppm, oxygen 14%, water 10%, and nitrogen (balance).

Table 1 shows the evaluation results of the NOx purification rate of the sample and the characteristics of β-type zeolite, that is, specific surface area S ₁ , outer surface area S ₂ , ion exchange amount M and M × (S ₂ / S ₁ ).

表１より、実施例１〜３のハニカムユニット１１’から切り出された試料は、ＮＯｘの浄化率が４９〜５０％であり、２００℃におけるＮＯｘの浄化性能が優れることがわかる。

From Table 1, it can be seen that the samples cut out from the honeycomb units 11 ′ of Examples 1 to 3 have a NOx purification rate of 49 to 50% and excellent NOx purification performance at 200 ° C.

On the other hand, the samples cut out from the honeycomb units of Comparative Examples 1 and 2 have NOx purification rates of 35% and 27%, respectively, and the NOx purification performance at 200 ° C. is inferior. This is because the ratio S ₂ / S ₁ of the outer surface area S _{2 to} the specific surface area S ₁ becomes small, that is, the number of pores existing on the surface of the zeolite increases, and the zeolite is not effectively used for purification of NOx. It is thought that.

  From the evaluation results of the NOx purification rate of the sample in Table 1, the NOx purification performance at 200 ° C. is excellent also in the honeycomb unit 11 ′ and the honeycomb structure 10 ′ of Examples 1 to 3 before cutting out the sample. Conceivable.

DESCRIPTION OF SYMBOLS 10, 10 'Honeycomb structure 11, 11' Honeycomb unit 11a Through-hole 11b Partition 12 Outer periphery coating layer 13 Adhesive layer 20 Holding sealing material 30 Metal container 100 Exhaust gas purification apparatus

The honeycomb structure of the present invention is a honeycomb structure having a honeycomb unit in which a plurality of through-holes are arranged in parallel in the longitudinal direction with a partition wall therebetween, and the honeycomb unit is an ion exchanged by iron ions And the raw material paste containing the inorganic binder is extruded, and then the extruded raw material paste is fired. The zeolite has a specific surface area of 500 m ² / g or more and 800 m ² / g or less. The surface area is 40 m ² / g or more and 80 m ² / g or less.

FIG. 1 shows an example of the honeycomb structure of the present invention. The honeycomb structure 10 includes a single honeycomb unit 11 in which a plurality of through holes 11a are arranged in parallel in the longitudinal direction with a partition wall 11b interposed therebetween. The honeycomb unit 11 is manufactured by extruding a raw material paste containing zeolite and an inorganic binder ion-exchanged with iron ions, and then firing the extruded raw material paste . Further, an outer peripheral coat layer 12 is formed on the outer peripheral surface excluding both end surfaces of the honeycomb unit 11.

Further, the honeycomb dried body is degreased to produce a honeycomb degreased body. The degreasing conditions can be appropriately selected depending on the type and amount of the organic substance contained in the dried honeycomb body, but it is preferably 2 hours at 400 ° C.

Next, the honeycomb unit 11 to which the outer peripheral coat layer paste is applied is dried and solidified to produce a columnar honeycomb structure 10. At this time, when the outer peripheral coat layer paste contains an organic binder, it is preferably degreased. The degreasing conditions can be appropriately selected depending on the type and amount of the organic substance, but it is preferably 20 minutes at 700 ° C.

In addition, instead of the zeolite ion-exchanged with iron ions, zeolite that is not ion-exchanged with iron ions is used to make the honeycomb unit 11 or the honeycomb structure 10 an aqueous solution containing iron ions (for example, an iron nitrate aqueous solution). The zeolite may be ion exchanged by immersing in it.

Next, an example of a manufacturing method of the honeycomb structure 10 ′ will be described. First, in the same manner as the honeycomb unit 11 of the honeycomb structure 10, a quadrangular columnar honeycomb unit 11 ′ is manufactured. Next, an adhesive layer paste is applied to the outer peripheral surface excluding both end faces of the honeycomb unit 11 ′, the honeycomb units 11 ′ are sequentially bonded, and dried and solidified to produce an aggregate of the honeycomb units 11 ′.

Next, a columnar honeycomb structure 10 ′ is produced by drying and solidifying the aggregate of columnar honeycomb units 11 ′ coated with the outer periphery coating layer paste. At this time, when an organic binder is contained in the adhesive layer paste and / or the outer peripheral coat layer paste, it is preferable to degrease. The degreasing conditions can be appropriately selected depending on the type and amount of the organic substance, but it is preferably 20 minutes at 700 ° C.

Next, the raw material paste 1 was extrusion-molded using an extruder to produce a regular quadrangular prism-shaped honeycomb formed body. Then, the honeycomb formed body was dried at 110 ° C. for 10 minutes using a microwave dryer and a hot air dryer, and then degreased at 400 ° C. for 5 hours. Next, the degreased honeycomb formed body was fired at 700 ° C. for 2 hours to produce a honeycomb unit 11 ′. The honeycomb unit 11 ′ was a regular quadrangular prism shape with a side of 38 mm and a length of 150 mm, the density of the through holes 11 a was 65 / cm ² , and the thickness of the partition walls 11 b was 0.28 mm.

Claims (14)

A honeycomb structure having a honeycomb unit in which a plurality of through holes are arranged in parallel in a longitudinal direction with a partition wall interposed therebetween, wherein the honeycomb unit is made of a raw material paste containing a zeolite ion exchanged by iron ions and an inorganic binder. The zeolite has a specific surface area of 500 m ² / g or more and 800 m ² / g or less, and an outer surface area of 40 m ² / g or more and 80 m ² / g or less. A featured honeycomb structure. The honeycomb structure according to claim 1, wherein the zeolite has an ion exchange amount of 1.6% by mass or more that is ion-exchanged with iron ions. When the ion exchange amount, specific surface area, and outer surface area that are ion-exchanged with iron ions of the zeolite are M [mass%], S ₁ [m ² / g], and S ₂ [m ² / g], respectively, The honeycomb structure according to claim 1, wherein 0.25 ≦ M × (S ₂ / S ₁ ) ≦ 0.60 is satisfied. The honeycomb structure according to any one of claims 1 to 3, wherein the zeolite has an average particle size of secondary particles of 3 µm or more and 5 µm or less. The honeycomb structure according to any one of claims 1 to 4, wherein the zeolite is β-type zeolite. The said raw material paste further contains 1 or more types selected from the group which consists of an inorganic fiber, a scale-like substance, a tetrapot-like substance, and a three-dimensional acicular substance, The Claim 1 thru | or 5 characterized by the above-mentioned. The honeycomb structure described. The honeycomb structure according to any one of claims 1 to 6, comprising a plurality of the honeycomb units. A method for manufacturing a honeycomb structure having a honeycomb unit in which a plurality of through holes are arranged in parallel in a longitudinal direction with a partition wall therebetween, and extruding a raw material paste containing a zeolite ion exchanged with iron ions and an inorganic binder And forming the honeycomb unit by firing the extruded raw material paste, wherein the zeolite has a specific surface area of 500 m ² / g or more and 800 m ² / g or less, and has an outer surface area of A method for manufacturing a honeycomb structure, wherein the manufacturing method is 40 m ² / g or more and 80 m ² / g or less. The method for manufacturing a honeycomb structure according to claim 8, wherein the zeolite has an ion exchange amount of 1.6% by mass or more that is ion-exchanged with iron ions. When the ion exchange amount, specific surface area, and outer surface area that are ion-exchanged with iron ions of the zeolite are M [mass%], S ₁ [m ² / g], and S ₂ [m ² / g], respectively, 10. The method for manufacturing a honeycomb structured body according to claim 8, wherein 0.25 ≦ M × (S ₂ / S ₁ ) ≦ 0.60 is satisfied. The method for manufacturing a honeycomb structure according to any one of claims 8 to 10, wherein the zeolite has an average particle diameter of secondary particles of 3 µm or more and 5 µm or less. The method for manufacturing a honeycomb structured body according to any one of claims 8 to 11, wherein the zeolite is β-type zeolite. The said raw material paste further contains 1 or more types selected from the group which consists of an inorganic fiber, a scale-like substance, a tetrapot-like substance, and a three-dimensional acicular substance, It is any one of Claims 8 thru | or 12 characterized by the above-mentioned. The manufacturing method of the honeycomb structure as described. The method for manufacturing a honeycomb structure according to any one of claims 8 to 13, wherein the honeycomb structure includes a plurality of the honeycomb units.

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